DE2459348A1 - METHOD FOR CATALYTIC CONVERSION OF HYDROCARBONS - Google Patents

Description

SHELL INTERNATIONAL RESEARCH MAATSCHAPPIJ B.V. The Hague, Netherlands

ⁿ Process for the catalytic conversion of hydrocarbons "

Priority: December 17, 1973, the Netherlands, no 7 317 235

The invention relates to a method for the catalytic conversion of hydrocarbons *
More particularly, the invention relates to the catalytic conversion of hydrocarbons to high viscosity index lubricating oils by hydrotreating a mixture of heavy hydrocarbons.

In the production of lubricating oils with a high viscosity index by hydrogenating cleavage of a mixture of heavy hydrocarbons, the compounds with a low viscosity index contained in the feed become compounds with a high viscosity index Viscosity index converted. At the same time, the levels of nitrogen, sulfur and oxygen in the oil are considerably reduced.

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The suitability of catalysts for use in the production of high viscosity index lubricating oils by means of hydro cracks of a mixture of heavy hydrocarbons depends on their temperature requirements and their aromatic retention capacity and their selectivity, which are defined as follows. Given the working conditions and when you are manufacturing of a lubricating oil with a predetermined viscosity index after dewaxing starts from a given feed, is understood by "temperature requirement" the temperature, which must be used to produce such a lubricating oil. The percentage understood in terms of aromatics contained in this lubricating oil, based on the aromatics content of the feed; under "selectivity" means the yield of the desired lubricating oil. The lower the temperature requirement and the aromatic retention

are
tevermögen the catalysts / and the higher their selectivity, the better the catalysts are suitable for the production of lubricating oils with a high viscosity index by hydrogenating splitting of a mixture of heavy hydrocarbons.

So far, a large number of catalysts have been proposed for the production of lubricating oils with a high viscosity index by hydrotreating a mixture of γοη heavy hydrocarbons. These catalysts generally contain one or more metals from groups VIB, VIIB and / or VIII or sulfides or oxides of these metals on a support material composed of one or more oxides of elements from group II,

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III or IV of the Periodic Table of the Elements. These catalysts can also be promoters, such as phosphorus or boron and contain a halogen such as chlorine or fluorine.

An in-depth study of the suitability of catalysts of the type described above for the production of lubricating oils with high Viscosity index by hydrocracking a mixture of heavy hydrocarbons has shown that their suitability for this purpose in an extraordinarily high degree of the type and amount of the metals incorporated into the carrier material and the Halogen and depends on the type of carrier material and its properties.

A number of catalysts of the type described above that have been investigated have proven completely unsuitable for the aforesaid Purpose proved, because of their temperature requirement and their

far

Aromatic retention / are too high while their selectivity is far too low. Most of the catalysts investigated turned out to be moderate for the aforementioned Purpose of use. Either the temperature requirement or the aromatics retention capacity or the selectivity of these catalysts is not sufficient for the best possible Catalyst behavior. However, a small group of catalysts of the type described above shows excellent performance in the production of high viscosity index lubricating oils by hydrotreating a mixture of heavy ones Hydrocarbons. The temperature requirement and the aromatic retention capacity these catalysts are very low while their selectivity is very high. Further investigations

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of the catalysts of the type described above for the production of lubricating oils with a high viscosity index by hydrogenative cracking of a mixture of heavy hydrocarbons showed that catalysts which show the best possible behavior for the purpose according to the invention are those described below Must meet conditions:

The finished catalyst must have a bulk density after compression of at least 0.8 g / ml and, in addition to fluorine, at least 3 parts by weight of nickel and at least 20 parts by weight of tungsten ■ Contains 100 parts by weight of aluminum oxide carrier material.

Under bulk density after compaction of the material is in the

an existing description of the quotient from / given amount of Material and its volume after extensive compression, the

particularly

/ is suitably effected by means of an electric vibrator.

The catalyst is made from an alumina hydrogel. An aluminum oxide hydrogel must be used, which is converted into a xerogel by drying and calcining leaves that has a bulk density after compaction of less than 0.8 g / ml. The way through which the catalyst is produced from this hydrogel in the individual case, depends on the pore volume quotient of the xerogel described above. The term "pore volume quotient" of a substance in the present Patent description of the quotient of the pore volume measured with mercury and the total pore volume of the Substance understood, whereby the pore size measured with mercury

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volume as the pore volume determined with mercury in pores with a diameter above 7.5 nm and the total pore volume as the sum of the pore volume present in pores with a diameter below 60 nm and determined with nitrogen and that in pores with a diameter of at least 60 nm existing pore volume determined with mercury are defined. If the pore volume quotient of the above-described xerogel is at least 0.5, the catalyst can in principle be produced in two ways, known as the "hydrogel route". and "Xerogelweg ^11. If the pore volume quotient of the above-described xerogel is less than 0.5, the preparation of the catalyst is suitably only possible in one of the two ways described above, namely via the" Hydrogelweg ".

The production of the catalysts via the xerogel route an alumina hydrogel, from which a xerogel can be made by drying and calcining, which has a bulk density after compaction of less than 0.8 g / ml and one Has a pore volume quotient of at least 0.5, is achieved by drying and calcining the aluminum oxide hydrogel, Incorporation of the metals and optionally the fluorine into the xerogel and drying and calcining of the mixture carried out.

The production of the catalyst via the hydrogel route from an aluminum oxide hydrogel, from which a xerogel by drying and Calcination can be produced, which has a bulk density after compaction of less than 0.8 g / ml and a pore volume

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quotients of at least 0.5 is achieved by incorporating the metals and optionally fluorine in the alumina hydrogel and drying and calcining of the mixture carried out,

The production of the catalysts via the hydrogel route from an aluminum oxide hydrogel, from which by drying and calcining a xerogel with a bulk density after compaction of less than 0.8 g / ml and a pore volume quotient of less than 0.5 is made by incorporating the metals and at least some of the fluorine into the alumina hydrogel and drying and calcining the mixture are carried out. In this production route of the catalyst is a such an amount of fluorine incorporated into the alumina hydrogel that the same amount of alumina hydrogel after drying and Calcination a xerogel with a pore volume quotient of at least 0.5 is obtained if this has the same amount of fluorine, but no metals, is (are) incorporated.

Except for the production of lubricating oils with a high viscosity index by hydrotreating a mixture of heavy ones The catalysts described above are suitable for hydrocarbons also for use in other processes in which hydrocarbons at. elevated temperatures and pressures and in the presence of hydrogen.

The present invention accordingly relates to a method for catalytic conversion of hydrocarbons, which is characterized in that the hydrocarbons are increased at

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Temperatures and pressures in the presence of hydrogen with a fluorine-containing nickel / Wolfrain catalyst on an aluminum oxide carrier material be contacted, which has a bulk density after compaction of at least 0.8 g / ml, the at least Contains 3 parts by weight of nickel and at least 20 parts by weight of tungsten per 100 parts by weight of carrier material and which, as described below, made from an alumina hydrogel is obtained by drying and calcining into a xerogel with a bulk density after compaction of less than 0.8 g / ml can be converted:

1) If the pore volume quotient of the xerogel described above is at least 0.5, the catalyst agent

a) drying and calcining the alumina hydrogel, Incorporate the metals and optionally the fluorine into the xerogel and dry and calcine the mixture or by means of

b) Incorporation of the metals and optionally the fluorine in the alumina hydrogel and drying and calcining the mixture

manufactured;

2) If the pore volume quotient of the xerogel is less than 0.5, the catalyst is activated by incorporating the metals and at least a portion of the fluorine in the alumina hydrogel and drying and calcining the mixture produced, with the proviso that in the latter case a

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such an amount of fluorine is incorporated into the hydrogel that a xerogel with a pore volume quotient is obtained by drying and calcining the same aluminum oxide hydrogel of at least 0.5 if this is the same. Amount of fluorine, but not metals, incorporated

will be).

For the production of catalysts which can be used according to the invention only certain aluminum oxide hydrogels are suitable. To determine whether to use an alumina hydrogel as a starting material for the preparation of catalysts which can be used according to the invention

over suitable, and, if so, to further determine which route to carry out the preparation of the catalyst. can, a sample of the hydrogel in question is ^{dried at 120 0} C and calcined ^{at 550 0 C.} The bulk density after compression and the pore volume quotient of the resulting xerogel are determined. The hydrogel is only suitable as a starting material for the production of catalysts suitable according to the invention if the xerogel produced from it has a bulk density after compression of less than 0.8 g / ml having. The pore volume quotient of the produced xerogel determines the way by means of which the production of the catalyst can be carried out. If the pore volume quotient of the xerogel produced is at least 0.5, the catalyst can be produced via both the xerogel and the hydrogel route. If the pore volume quotient is less than 0.5, only the hydrogel route is suitable for producing the catalyst, whereby it must be ensured that the

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BATH ORIGINAL

Preparation of the catalyst via the hydrogel route, a sufficient amount of fluorine is incorporated into the hydrogel. The minimum amount of fluorine which has to be incorporated in the preparation of the catalyst in the hydrogel can be determined by different amounts of fluorine in a series of samples of the corresponding hydrogel incorporating Urid the industrial containing hydrogel at 120 ⁰ C dried and calcined at 550 ⁰ C calcined. The pore volume quotient of the resulting corridor-containing xerogel is then determined. The aforementioned minimum amount of fluorine that must be incorporated into the hydrogel is that which leads to a corridor-containing xerogel with a pore volume quotient of 0.5. ·. -

If the catalysts which can be used according to the invention over the The aluminum oxide hydrogel is used to produce xerogel

are first dried and calcined, then / the metals and optionally fluorine incorporated into the calcined material, and the resulting mixture is finally dried and calcined. The incorporation of the metals into the calcined Material can particularly expediently by impregnating the calcined material with an aqueous, nickel and a solution containing tungsten compound. Fluorine can be incorporated into the catalyst either by impregnation or by in-situ fluorination. If fluorine in the Catalyst is incorporated by means of impregnation, this can either together with nickel and tungsten or in a separate. derten impregnation stage with an aqueous solution of a Fluorine compound can be carried out. The incorporation of fluorine

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in the catalyst by means of impregnation is preferably in a separate impregnation stage after the incorporation of Nickel and tungsten carried out into the calcined material and after calcining the impregnated material again. The in-situ fluorination of the catalyst can be carried out by adding a given amount of a fluorine compound during the initial stage of the process in which the catalyst is used to the gas and / or liquid stream which is passed over the catalyst, added until the required Fluorine content of the catalyst has been reached. If in the method carried out according to the invention an over The catalyst produced by the xerogel route is used, a catalyst is preferably used in which at least some of the fluorine and in particular practically all of the fluorine has been incorporated by in situ fluorination.

If the catalysts which can be used according to the invention have been prepared by the hydrogel route, the metals and optionally the fluorine is incorporated into the hydrogel and the resulting mixture is then dried and calcined. Incorporation of the metals into the hydrogel can particularly

conveniently by treating the hydrogel with a

containing an aqueous / nickel and a tungsten compound

Solution to be carried out. This treatment is preferred. carried out at a temperature above 50 ⁰ C and especially at temperatures of 60 to 25O ⁰ C. Fluorine can be incorporated into the catalyst while the aluminum oxide is still in hydrogel form, or after calcination of the mixture obtained and also by in-situ fluorination.

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Incorporation of the fluorine into the catalyst while the aluminum oxide is still in the hydrogel form is preferred by treating the hydrogel with an aqueous compound, a nickel compound, a tungsten compound and a fluorine compound containing solution carried out. If in the method according to the invention one produced by the hydrogel route Catalyst is used, a catalyst is preferably used, in the .at least part of the fluorine and in particular practically all of the fluorine has been incorporated into the aluminum oxide, which is still in the hydrogel state.

Catalysts suitable according to the invention contain at least 3 parts by weight of nickel and at least 20 parts by weight of tungsten per 100 parts by weight of aluminum oxide.

If the catalyst has been produced via the xerogel route a catalyst is preferably used which contains 3 to 12 parts by weight of nickel and 20 to 75 parts by weight of tungsten contains per 100 parts by weight of aluminum oxide and in particular a catalyst that also contains nickel and tungsten in one weight contains a ratio of 1: 5 to 1: 7. The catalysts prepared by the xerogel route preferably contain 0.5 to 20 parts by weight of fluorine per 100 parts by weight of aluminum oxide, with the proviso that when these catalysts are used for the production of lubricating oils with a high viscosity index by hydrotreating a mixture of heavy Hydrocarbons, catalysts with a fluorine content of preferably 0.5 to 10 parts by weight per 100 parts by weight of AIu-

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miniumoxide can be used while using these catalysts for the production of light hydrocarbons by hydrotreating a mixture of heavy hydrocarbons the fluorine content of these catalysts is preferably 10 to 20 parts by weight per 100 parts by weight of aluminum oxide amounts to.

Catalysts produced by the hydrogel route preferably contain 25 to 50 parts by weight of nickel and 50 to 60 parts by weight of tungsten per 100 parts by weight of aluminum oxide and in particular Catalysts are used which also have a weight ratio of nickel to tungsten between 1 to 1.5 and 1 to 5 exhibit. The catalysts prepared by the hydrogel route preferably contain 10 to 30 parts by weight of fluorine per 100 parts by weight Aluminum oxide, with the proviso that when using these catalysts, for the production of lubricating oils with a high Viscosity index due to hydrocracking of a mixture of heavy hydrocarbons, preferably the soil content of these catalysts 10 to 25 parts by weight per 100 parts by weight of aluminum oxide, while these catalysts in use for the production of light hydrocarbons by hydrogenative splitting of heavy hydrocarbons a fluorine content of preferably 20 to 30 parts by weight per 100 parts by weight of aluminum oxide.

While the starting material for the production of the invention Suitable catalysts used hydrogels have the characteristic property that xerogels from them with a bulk density after compaction of less than 0.8 g / ml

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2A59348

can be obtained by drying and calcining, show the catalysts prepared on the basis of these hydrogels a bulk density after compaction of at least 0.8 g / ml. Accordingly, a must during the preparation of the catalyst Increase in bulk density can be brought about after compaction. An increase in the bulk density after compaction occurs among other things when the metals are incorporated, and the greater the incorporated metal load, the greater it is. An increase the bulk density after compaction is also determined by compacting the hydrogel, e.g. by kneading, pressing or extruding, brought about, "the increase in bulk density increases after compaction with higher applied pressures. A substantial ZunaTime of the bulk density after compaction can be can be brought about by pressing the hydrqgel under high pressure through a narrow opening, such as a slit. By Exercise of pressure-induced increase in bulk density after compaction of the hydrogel can be made even further by incorporation certain additives in the hydrogel, such as that of nitric acid and aluminum salts.

In addition to fluorine, the catalysts suitable according to the invention can be used also contain other promoters such as phosphorus and boron.

The metals nickel and tungsten can be used in the invention .suitable catalysts as such or in the form of their oxides or sulfides are present. Preference is given to using catalysts which contain the metals in sulfidic form. The sulfidation of the catalysts suitable according to the invention

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can be sulfided by any known method be carried out by catalysts. The sulfiding can be carried out, for example, by contacting the catalyst with a sulfur-containing gas such as a mixture of hydrogen and hydrogen sulfide. The sulphiding can expediently also by contacting the catalyst mit.einöm sulphurous hydrocarbon oil, such as a sulphurous gas oil.

The catalysts according to the invention are of particular importance in the production of lubricating oils with a high viscosity index. by hydrospalling a mixture of heavy hydrocarbons. Preferably as the starting material for the production of lubricating oils by means of the inventive method, mixtures used heavy hydrocarbon paraf f inhaltige lubricating oil fractions, which have been obtained in the distillation at reduced pressure a residue · obtained at atmospheric pressure distillation of a paräffinhaltigen crude oil and paraffins from these paraffin-containing lubricating oil fractions or from paraffin-containing lubricating oil fractions obtained by means of hydrogenation cracking. Examples of such paraffin-containing lubricating oil fractions

paraffinic distillates for

are / spindle oil (EO), light machine oil (LMO) and medium heavy machine oil (14M0), and deasphalted oils (DAO), paraffinic SO- LMO- and MMO-Raf f i- nate and paraffinic bright stocks (BS) consisting of the the aforesaid lubricating oil fractions, obtained by treating the latter with a selective solvent for aromatics such as furfural , and SO-, LMO-; MMO-; DAO and BS paraffin

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gatsche obtained from the aforementioned lubricating oils by dewaxing have been manufactured. Mixtures of one or more lubricating oil fractions obtained as a distillate and / or one or more residual lube oil fractions and / or one or more paraffinate may also be seen as Starting material can be used for the production of lubricating oils by means of the method according to the invention.

The hydrogenative cracking of a mixture of heavy hydrocarbons for the production of lubricating oils with a high viscosity index by means of the method according to the invention by contacting the mixture of heavy hydrocarbons at elevated temperatures and pressures and in the presence carried out of hydrogen with the catalyst suitable according to the invention, preferably in one or more beds consists of catalyst particles with diameters of 0.5 to 3 mm. · '

Suitable conditions for hydrogenating columns are temperatures from 325 to 450 ⁰ C, pressures from 10 to 250 bar, a ratio of Viasserstoff to feeding in from 100 to 5000 Nl of hydrogen per kg feed, and a Raümströmungsgeschwindigkeit of 0.2 to 5.0 kg feed per Liters of catalyst per hour. Temperatures of 350 to 425 ° C., pressures of 100 to 200 bar, a ratio of hydrogen to feed of 500 to 2500 Nl of hydrogen per kg of feed and room flow rates of 0.5 to 1.5 kg of feed are preferred

applied per liter of catalyst per hour.

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Lubricating oils produced by means of the process according to the invention have a low aromatic content. Lubricating oils with An even lower aromatic content can be produced according to the invention if, after the hydrogenative cleavage, a Post-hydrogenation is carried out. The post-hydrogenation of the product obtained in the hydrogenative cleavage can be carried out by contacting this product at elevated temperatures and pressures in the presence of hydrogen with a post hydrogenation catalyst be performed. The pressures, space flow velocities and gas velocities used in the post-hydrogenation stage -comply with the aforementioned conditions for the hydrating spa2img. . Preferably

be applied to the post-hydrogenation temperatures 225-400 ⁰ C and in particular 275-375 ⁰ C. The applied in the post-hydrogenation temperature should be at least 25 ⁰ C under the applied when hydrogenating column temperature. Suitable post-hydrogenation catalysts are catalysts containing one or more metals from groups VIB, VIIB or VIII on a support material.

The product withdrawn from the reactor for hydrogenation and, if post-hydrogenation is used, the product withdrawn from the reactor for post-hydrogenation, is cooled and separated into a hydrogen-rich gas and a liquid product. The liquid product contains hydrocarbons that boil below the boiling range of the lubricating oil and hydrocarbons that boil within the boiling range of the lubricating oil. The hydrocarbons boiling below the aforementioned range are removed from the higher-boiling residue, preferably by means of frac-

o u b ο ζ b / u y ρ y

ORIGINAL INSPECTED

.- 17 -

separated distillation. The intersection of this distillation is preferably chosen so that the higher-boiling residue has an initial boiling point of 350 to 55O ⁰ C. In addition to excellent lubricating oil components, this residue generally contains straight-chain paraffins which solidify at room temperature and therefore worsen the pour point of the lubricating oil. In order to produce a suitable lubricating oil from this residue, the residue is therefore preferably dewaxed. The dewaxing treatment can be carried out in any manner. The dewaxing is preferably carried out using a mixture of methyl ethyl ketone and toluene at temperatures from -10 to -40 ° C. and using a volume ratio of solvent / oil of 11.1 to 10: 1. In order to increase the yield of lubricating oil, at least some of the separated paraffins are returned to the hydrocracking reactor.

In addition to being used as catalysts for the hydrogenative cleavage of a mixture of heavy hydrocarbons for the production of lubricating oils with a high viscosity index, the catalysts that can be used according to the invention are also particularly suitable as catalysts for the first stage of a two-stage process for the production of light hydrocarbons, such as gasoline and kerosene, by hydrogenating .Spalten a mixture of heavy hydrocarbons, such as gas oils, flash distillates and mixtures of flash distillates and deasphalted oils. Examples of other processes according to the invention in which the above-described catalysts are successful

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The production of light hydrocarbons from a mixture of heavy hydrocarbons can be used in abundance by single-stage hydrogenation splitting, the hydrogenation of those contained in light fuels such as kerosene Aromatics to improve their smoke point, the hydrogenating desulphurisation of distillate and residual hydrocarbon fractions, the rehydration of lubricating oils and the · production of technical white oils and medicinal oils Oiling through the catalytic hydrogenation of a mineral oil fraction low in aromatic compounds.

The examples illustrate the invention.

A total of 37 catalysts are used in the conversion of hydrocarbon oils at elevated temperatures and pressures and checked in the presence of hydrogen. Of these 37 catalysts 19 represent suitable catalysts according to the invention (catalysts 1 to 19), while the other 18 catalysts (Catalysts A to T) are not suitable for the process according to the invention. The manufacture of the catalysts is performed as described below.

Catalysts 1 to 13

These catalysts are produced via the xerogel route from an aluminum oxide hydrogel which, after drying and calcining, produces a xerogel with a bulk density after compaction of 0.35 g / ml and a pore volume quotient of 0.8. (Aluminum oxide hydrogel I) results.

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The preparation of the catalysts 1 to 7 is carried out by drying, extruding and calcining the aluminum oxide hydrogel I,

Impregnating the extrudates with an aqueous solution containing a nickel and a tungsten compound and drying and Calcining the impregnated extrudates carried out.

The production of catalyst 8 is carried out by means of drying, extrusion

dieren and calcination of the aluminum oxide hydrogel I, impregnation of the extrudates with an aqueous, a nickel, a A solution containing tungsten and a boron compound, and drying, and calcining of the impregnated extrudates are carried out.

The fluorine is added to catalysts 1 to 8 by means of in-situ fluorination incorporated.

The production of the catalysts 9 to 13 is carried out by drying, extruding and calcining the aluminum oxide hydrogel I, Impregnating the extrudates with an aqueous solution containing a nickel and a tungsten compound, drying and Calcining the impregnated extrudates, impregnating the calcined extrudates with an aqueous, fluorine compound containing solution and drying and calcining of the impregnated extrudates carried out. An extra amount of fluorine is converted into catalysts 10 to 13 by means of in situ fluorination incorporated.

Catalysts 14 to 19

These catalysts are made via the hydrogel route. The catalysts 14 to 17 are made of the aforementioned aluminum

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nium oxide hydrogel I produced. The catalysts 18 and 19 are made from an aluminum oxide hydrogel which, after drying and calcining, forms a xerogel with a bulk density after compression of 0.7 g / ml and a pore volume quotient of 0.3 results (aluminum oxide hydrogel II).

The preparation of catalyst 14 is accomplished by blending an aqueous one containing a nickel and a tungsten compound Solution with the aluminum oxide hydrogel I and by keeping the mixture at an elevated temperature for a certain time, Separating the hydrogel loaded with the metals from the mixture and then drying, extruding and calcining of the aforementioned hydrogel carried out. Fluorine is incorporated into the catalyst 14 via in-situ fluorination.

The preparation of the catalysts 15 to 19 is carried out by means of mixing an aqueous solution containing a nickel, a tungsten and a fluorine compound with either the alumina hydrogel I (for the production of the catalysts 15 to 17) or the aluminum oxide hydrogel II (for the production of the catalysts 18 and 19) by holding the mixture for some time at an elevated temperature, separating the with the metals and fluorine-loaded hydrogel from the mixture and then drying, extruding and calcining the above Hydrogel carried out. An additional amount of fluorine is incorporated into catalysts 16, 17 and 19 by in-situ fluorination.

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Catalysts A to E

These catalysts are obtained from the aforementioned via the xerogel route Alumina Hydrogeleri I and II produced.

The preparation of the catalysts A and B is carried out by drying, extruding and calcining either of the 'aluminum oxide hydrogeis ■ I "* (for the production of catalyst A) or the aluminum oxide hydrogel II (for the production of catalyst B), impregnation of the extrudates with an aqueous, a nickel, and / or Solution containing tungsten compound and drying and calcining of the impregnated extrudates. Fluorine is incorporated into catalysts A and B by in situ fluorination.

The catalysts C to E are impregnated by means of drying, extruding and calcining the aluminum oxide hydrogel II
the extrudates with an aqueous solution containing a nickel and a tungsten compound, drying and calcining
the impregnated extrudates, impregnating the calcined extrudates with an aqueous solution containing a fluorine compound, and drying and calcining the impregnated extrudates. An additional amount of fluorine is incorporated into catalysts D and E by in situ fluorination »

Catalysts F and G

These catalysts are from the above-described via the hydrogel route Aluminum oxide hydrogel Ιΐ-made.

The catalyst F is by mixing an aqueous, a

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Nickel and a tungsten compound containing solution with the Alumina hydrogel II and. Holding the mix for some Time at elevated temperature, separation of the hydrogel loaded with the metals from the mixture and subsequent drying, Extruding and calcining the hydrogel described above. Fluorine is incorporated into the catalyst F by means of in situ fluorination.

The catalyst G is obtained by mixing an aqueous solution containing a nickel, a tungsten and a fluorine compound with the aluminum oxide _r Hydrogel II and keeping the mixture for some time at an elevated temperature, separating the hydrogel loaded with the metals and fluorine from the mixture and subsequent drying, extruding and calcining of the hydrogel described above. An additional amount of fluorine is incorporated into catalyst G by in-situ fluorination.

Catalysts H to T

These catalysts are made by impregnating a calcined support material with an aqueous, one or two metal compounds and optionally a solution containing a boron or phosphorus compound, followed by drying and calcining of the mixture formed.

The catalyst H is made by impregnating a silica-zirconia support material with an aqueous solution containing a platinum compound and then drying and calcining the mixture.

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The catalysts J to M are made by impregnating an aluminum oxide carrier material with an aqueous solution containing a nickel, a molybdenum and a phosphorus compound and then drying and calcining the mixture. Fluorine is incorporated into the catalysts K to M by in situ fluorination.

The preparation of catalyst N is carried out by impregnating an aluminum oxide carrier material with an aqueous, a Containing nickel, a tungsten and a boron compound Solution and subsequent drying and calcining of the mixture formed.

The "catalysts P to R" are made by impregnating either an aluminum oxide carrier material (for the production of Catalyst P), or a silica-alumina support material (for making Catalyst Q), or a silica-magnesia carrier material (for making of catalyst R) with an aqueous solution containing a nickel and a tungsten compound and then the solution Drying and calcining the mixture produced.

The production of the catalysts S and T is carried out by impregnating a fluorine-containing aluminum oxide carrier material with an aqueous solution containing a nickel and either a tungsten compound (for producing catalyst S) or a molybdenum compound (for producing catalyst T) and then drying and Calcining the mixture carried out. _s "g" _{2 5} , "g. _B ,

The chemical composition and some other values of the various catalysts are listed in Tables A and B. . '

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Tabel

Catal
gate

Catalyst composition in parts by weight per 100 parts by weight Aluminum oxide support material

Route used to prepare the catalyst

Ni

Used to make the catalyst Alumina hydrogel

Xerogel hydrogel

II

Percentage of the
the catalyst
incorporated by in situ fluorination
Fluorine content

Bulk density of the catalyst after compression,

g / ml

1 Ul 30th 6th cn
ο CVl Ul 30th ■ 15 co
CX) - 3 Ul 30th 10 cn
■ - 7.5 _t 45 15th 6960 5.
6th 10 '
10 ' 6C .15
15th 7th 3 »5 30th 15th 8th* ^r ) 7.9 35, 8 1 9 LfV 30th 6th IC UI 30 ^ 6th 11 • 5, 30th • 6 12th IC 60 ■ 15 13th Ίο 60 15th

100
100
100
100
100
100
100
100
0

• 25
75
80
60

0.9 0.9 0.9 0.9 1.0

0.9 ■ 0.9

0> 9

0.9 0.9 0.9

i, o '

1.0

Table A (continued)

Catalyst composition in ^{parts by} weight per 100 parts by weight of aluminum oxide support material

Route used to prepare the catalyst

Alumina hydrogel used to make the catalyst

Ni

Xerogel hydrogel

Percentage of the catalyst by ^ in - situ fluorination incorporated -Fluorgehalts

Bulk density of the catalyst after compaction,

g / ml

50982 Ik
15th
16 37 _p
37
37 70
70
70 ' Ik cn
σ
co
ό> 17th
18 **) 37
37 70
70 Ik
Ik co 19 **) 37 70 ■ Ik A. '2.5 1.5 15th E. VJl 30th £ C. 5 30th 6th D. VJI 30th β E. 5 30th ^{; <} 6 P. 37 70. Ik Sill. 27 70 Ik

100 0

25th

75

25th

10.0

1ST FLOOR

25th

75

100

1.3

1.5 0.7 1.2 1.2 1.2 1.2 ■ * · »- ■

Ol CO CO

'- 27 footnotes from Table A:

*) Catalyst 8 additionally contains 4 parts by weight of boron per 100 parts by weight of aluminum oxide support material.

**) In the hydrogels that make up the catalysts 18, 19 and G have been produced, such an amount of fluorine is incorporated that the pore volume quotient of the xerogels, which can be prepared from these fluorine-containing hydrogels by drying and calcining, 0.7; 0.6 or Is 0.4.

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Table B - page 28 -

ι «

Catalyst composition-in parts by weight tr _e f, i, rcofnr.

l ^ sa- ^Meta11 J ^{e 10} ° parts by weight of catalyst- T? äS? rierIal

gjT carrier material carrier material

No. '; :

Ni Mo W Pt P B F

SiO ₂ ZrO ₂

S ■ ^K 3.8 16.0 .4 3

in ^ *

2.5. Al ₂ O

«> M- IC 20. "· 2 2

K 3 , C 10, 5 35 0.6 1.8 J. 3 /8th' 16, 0 26th 4th K 2 , 7 15, 6th 11 2 L. IC 20th 11 2 M- 7th , 9 11 N n , 9 lh , δ '" P ' 2 , 3 , 3 Q 3 .5- , 0 R. 2 , 3 , 0 S. 2 , -3 , 0 Γ

2 5 Al η <"

* ,:> ^Hx 2 "3 'co

Ca) OO

Example 1

The temperature requirement, the Aroinatenrückhaltevermögen and the selectivity of a number of catalysts used in Table A for the preparation of an above 400 ⁰ C boiling lubricating oil having a viscosity index of 130 to dewaxing 'at -30 ⁰ C are compared in a HydrospaltungsversuGh each other, the under the conditions described below Conditions is carried out:

Feed:

Oil produced from a deasphalted residue obtained by distillation under reduced pressure of a residue from the atmospheric pressure distillation of a Middle Eastern crude oil.

Properties of the feed:

Viscosity index after dewaxing at -30 ⁰ C 77 Sulfur content: 2.1 percent by weight Nitrogen content: 0.063 percent by weight aromatic content: 135 mmol / 100 g hydrocracking conditions:

Pressure: 150 bar

-1-1 Room air velocity: 1 1.1. Hour Ratio of hydrogen to feed: 2000 Nl.1.

The catalysts are used in sulfidic form. The sulfiding of the catalysts is carried out by this 5 hours with a mixture of hydrogen and sulfur

509825/0969 -

Hydrogen with a volume ratio of 7: 1 at a temperature between 75 and 375 C and a pressure of 10 bar coherently clocked.

The dewaxing is carried out with a 1: 1 mixture of methyl ethyl ketone and toluene. The in-situ fluorination of the appropriate catalysts is accomplished by adding 0.03 percent by weight Fluorine in the form of o-fluorotoluene for feeding carried out during the initial phase of the experiment until the required fluoro content of the catalyst has been achieved. The catalysts are tested in the form of 1.5 mm extrudates,

In this experiment, the best possible catalyst has a temperature requirement of at most 42O ⁰ C, a Aromatenrückhaltevermögen of at most 30 percent, and a selectivity of at least 35 weight percent.

The results of this experiment are summarized in Table C.

509825/0969

Tabel

No. of ge
checked
Catalyst temperature
requirement , Selectivity,
Weight pro
cent of
Feed Aromatic
Restraint
be able to
percent 9 HlQ '35 • '15 10 ■ ' HlS 35 12th 11 St. 35 9 1 • 412 35 8th 15th 403 39 7th 16 408 • 38 7.5 17 · 4114 36 9 14th 418 '36 15th C. ■ 431 ■ 32 31 D. 429 33 '26 E · · 422 33. "Ϊ9 B. 420 33 17th 18th 403 39 7th 1'9 411 36 8th G- 413 30th 11 F. 29 11

509825 / 096.9

Example 2

The temperature requirement, the aromatic retention capacity and. the selectivity of a number of the catalysts listed in Tables A and B for the preparation of an above 375 ⁰ C boiling lube oil having a viscosity index of after dewaxing at -2O ⁰ C are joined in a n ". Compared hydrocracking test, which is carried out under the same conditions as in Example l.

Feed:

oil, received. . by deasphalting a residue from the Reduced pressure distillation of an atmospheric pressure residue of a Middle Eastern crude oil.

Properties of the feeding in: Viscosity Index after dewaxing at -2O ⁰ C 81 Sulfur content: 2.5 percent by weight Nitrogen content: 0.078 percent by weight aromatics: 100 n.Mol / 100 g

Catalyst bed: 100 ml.

The catalysts are in the form of particles with a diameter tested from 0.5 to 1.4 mm.

In this test, the best possible catalytic converter has a temperature requirement of no more than 420 C. Aromatic retention capacity of at most 30 percent and a selectivity of at least 40 percent by weight. The results of this experiment are summarized in Table D.

509825/0989

Tabel

No. of
checked
■ catalyst

Temperature requirement,

Or,

Selectivity,
Weight percent
the feed

Aromatic retention capacity,
percent

1 410 15th 400 H*) 440 J 433 P. ■ 435 Q . 421 R. 413 S. 426 τ- '424

44
48
36
38
38
40
38
43
43

*) Under the conditions used in this test It was not possible to use lubricating oils with a viscosity index of 128 using a catalyst H to produce. The values given in Table D for catalyst H relate to the preparation a lubricating oil with a viscosity index of 112.

509825/0969

Example 3

The temperature requirement and the selectivity of a number of catalysts listed in Tables A and B for the production of a ^{lubricating oil boiling above 43O 0} C with a viscosity index of 96 after dewaxing at -20 ⁰ C v / earth compared with each other in a hydrocracking test, the below is carried out under the conditions described below.

Feed:

Paraffinic heavy distillate lubricating oil fraction of a Middle Eastern crude oil.

Properties of the feed:

Viscosity index after dewaxing at -20 ⁰ C 37 Sulfur content: 3 weight percent
Nitrogen content: 0.125 percent by weight.

Hydrocracking Conditions:

Hydrogen partial pressure: 140 bar

—1 -1 Space velocity: 1 kg.l. Hour.

Ratio of hydrogen / feed :. 2000 Nl.kg " Catalyst bed: 250 ml.

The catalysts are examined in the form of 1.5 mm extrudates.

During sulphidation and in-situ fluorination of the catalysts and when the oils are dewaxed, the same

509825/0969 -

conditions _y as in Example 1, applied.

In the present test may best possible catalyst has a temperature requirement of a maximum of 405 ⁰ C and a selectivity of at least 51 percent by weight.

The results of this experiment are given in Table E.

509 825/0989

- Page 36 Table E.

No. of the tested temperature requirement, selectivity,

Light process] feed

Catalyst ° C · weight percent of

σ 15 '39 ¹ »' ■ 53

CD '.

oo _l8 397 52

K 402 'H9

L '405 49

■ T

μ 410. 49

N 405. 49

Ul CD CO

example

A number of the catalysts described in the Tables A and B are used in a hydrocracking experiment of producing a boiling above 390 C lubricating oil having a viscosity index of 150 after dewaxing at -30 ⁰ C.

Feed:

Brightstock slack wax

Feed characteristics: Oil content: 30 percent by weight. Sulfur content: 0.73 percent by weight Nitrogen content: 0.0086 percent by weight

Under the hydrocracking conditions described below, 70 percent by weight of the paraffin is converted.

Hydrogen partial pressure: 130 bar

-1 -1

Room flow velocity: 1 kg / hour.

Ratio of hydrogen / feed: 1500 Nl.kg Catalyst bed: 250 ml.

"The catalysts are used in the form of 1.5 mm extrudates. ..

The sulfiding and in-situ fluorination of the catalysts and the dewaxing of the oils is carried out under the same conditions as carried out in Example 1.

ν 509825/0989

The results of this test are summarized in Table F.

Table F.

No. of the tested Lube oil yield, Catalyst Weight percent 1 HO 8th ■ 39 15th 40 18th HO , .K 3't L 33 M. . _ 35

The results of Tables C to F show the superiority of the catalysts which can be used according to the invention (catalysts 1 to 19) in the production of lubricating oils with a high viscosity index due to hydro cracks compared to the closely . related, not according to the invention suitable catalysts (catalysts A to G) and compared to others so far for the preparation of lubricating oils by means of hydro cracks (catalysts H. to T) clearly stand out.

509825/0960

Example 5

A number of the catalysts listed in Table A are used in the first stage of a two step process for preparation of gasoline and middle distillates used by hydrocracking a heavy hydrocarbon oil '.

Feed:, '

Flash distillate of a Middle Eastern crude oil.

Properties of the feed:

Initial boiling point: 300 ^° C

Final boiling point: 520 ° C

28 percent by weight of the feed boils below 370 ° C

Nitrogen content: 0.065 percent by weight, polyaromatic content: 60 mmol / 100 g

Hydro splitting conditions: -

Temperature: 370 ⁰ C. ·

Pressure: 130 bar

-1 - T space velocity: 1.7 1.1 .h.

Ratio of hydrogen / feed: 1000 Nl. 1

The catalysts are used in sulfidic form. The sulfidation of the catalysts is carried out by contacting for 1-6 hours with a mixture of hydrogen and hydrogen sulfide with a volume ratio of 7: 1 at temperatures of 75 to 450 ^° C. and pressures of 10 bar. The in situ fluorination of the catalysts is carried out by adding 0.2 percent by weight of fluorine in the form of fluorotoluene

509825/0969

Feed during the initial phase of the experiment until it is reached the fluorine content required for the catalyst. The catalysts are in the form of 1.5 mm extrudates checked.

The results of this experiment are summarized in Table-G.

509825/0969

Tabel

No. of the tested
Catalyst Nitrogen content
of the liquid pro.
dukts,
Weight percent Polyaromatic content
of the liquid pro
dukts,
. 'mmol / 100 g . Share in under
half 370 ⁰ C they
the liquid
Product,
Weight percent ro cn
ο 2 0.0004 ^ 3 ; 593 CD
00 3 ■. 0.0012 5 • '41 4 '■ 0.0004 ■ 3.5 43 0969 5:
ι
6th . 0.0004
0.0007 2 43 -c '
41 7th 0.0013 6th 42 12th 0.0004 2 '. ^a 3 13th 0.0004 2 43 'A Ό, ΟΟβΟ 10

The results in Table G clearly show the superiority of the catalysts suitable according to the invention (catalysts 2 to 7, 12 and 13) when used as catalysts in the first stage of a two-stage process for making gasoline and middle distillates versus a very similar catalyst (catalyst A) which is not suitable according to the invention. The latter catalyst, the too low a nickel and tungsten loading and too low a bulk density after compaction leads to a less removal of nitrogen and polyaromatics and a lower degree of cleavage than those suitable according to the invention Catalysts. ■

50 9 825/0 969

Claims (22)

- 43 claims: 1. Process for the catalytic conversion of hydrocarbons, characterized in that the hydrocarbons are at elevated temperatures and Pressing in the presence of hydrogen with a fluorine-containing nickel / tungsten catalyst on an aluminum oxide support material be contacted, which has a bulk density after compaction of at least 0.8 g / ml to v / eist, the at least 3 parts by weight of nickel and at least 20 parts by weight of tungsten per 100 parts by weight of carrier material contains one and, as described below, made of / aluminum • - nium oxide hydrogel that is produced by drying and calcining converted to a xerogel having a bulk density after compaction of less than 0.8 g / ml can be: 1) If the pore volume quotient of the above Xerogels is at least 0.5, the catalyst is means a) drying and calcining the alumina hydrogel, Incorporation of the metals and optionally the fluorine into the xerogel and drying and calcining of the Mixture, or by means of b) Incorporation of the metals and optionally the fluorine into the aluminum oxide hydrogel and drying and calcining of the mixture made; 50 9 8 25/09 89 2) -If the pore volume quotient of the xerogel is less than 0.5, the catalyst is incorporated by means of of the metals and at least some of the fluorine into the alumina hydrogel and drying and calcining of the mixture produced, with the proviso that in the latter case, such an amount of fluoro in "The hydrogel is incorporated that you can by drying and calcining from the same alumina hydrogel a xerogel with a pore volume quotient of at least 0.5. obtained when the same amount of fluorine, but no metals, is incorporated (will). 2. The method according to claim 1, characterized in that a catalyst is used which is via the xerogel route has been produced and the 3 to 12 parts by weight Nickel and 20 to 75 parts by weight of tungsten per 100 parts by weight of aluminum oxide. 3. The method according to claim 2, characterized in that a catalyst is used, the nickel and tungsten contains in a weight ratio of 1: 5 to 1: 7. 4. The method according to claim 1 to 3 »characterized in that that a catalyst is used "which has been produced by the xerogel route and which contains 0.5 to 20 parts by weight of fluorine per 100 parts by weight of aluminum oxide. 509826/0969 5. The method according to claim 1 to 4, characterized in that a catalyst is used which is via the xerogel route has been produced, and in which at least some of the fluorine and preferably all of the fluorine by " in situ fluorination has been incorporated. 6. The method according to claim 1, characterized in that a catalyst is used which has been prepared via the Hydrogelweg, and during its production the incorporation of the metals into the Hydrogex by treatment of the hydrogel at a temperature above 50 ⁰ C and preferably at temperatures from 60 to 250 ⁰ C with an aqueous solution containing a nickel and a tungsten compound has been carried out. 7. The method according to claim 1 to 6, characterized in that that a catalyst is used which has been prepared by the hydrogel route and which is 25 to 50 percent by weight Nickel and 50 to 80 percent by weight tungsten per 100 parts by weight of aluminum oxide. 8. The method according to claim 7, characterized in that a catalyst is used, the nickel and tungsten in a weight ratio of 1: 1.5 to, 1: 5 contains. 9. The method according to claim 1 and 6 to 8, characterized in that a catalyst is used which is about the hydrogel route has been made and the 10 bis Contains 30 parts by weight of fluorine per 100 parts by weight of aluminum oxide. 509 8 25/0969 10. The method according to claim 1 and 6 to 9, characterized in that . that a .catalyst is used, which has been produced by the hydrogel route, and in its Production of at least some of the fluorine and preferably all of the fluorine into that which is still present in hydrogel form Aluminum oxide has been incorporated. 11. "The method according to claim 1 to 10, characterized in that a catalyst is used which the metals in contains sulfidic form. 12. The method according to claim 1 to 11, characterized in that a lubricating oil mit.hohem viscosity index through hydrogenative splitting of a mixture of heavy hydrocarbons is produced. 13 · Method according to claim .1. to 5 and 11, characterized in that a catalyst is used for the production of lubricating oils by hydrotreating a mixture of heavy hydrocarbons which has been produced via the xerogel route and which contains 0.5 to 10 parts by weight of fluorine per 100 parts by weight of aluminum oxide. 14. The method according to claim 1 and 6 to 11, characterized in that that for the production of lubricating oils by hydrogenative splitting of a mixture of heavy hydrocarbons a catalyst is used that is over ■ the hydrogel route has been established and the 5098 25/0969 10 to 25 parts by weight of fluorine per 100 parts by weight of aluminum oxide. 15. The method according to claim 1 to 14, characterized in that lubricating oils with a high viscosity index by hydrogenating Splitting a mixture of heavy hydrocarbons out of the group a) paraffinic, when distilling at reduced Pressure of a residue obtained from the atmospheric pressure distillation of paraffin-containing crude oils Lubricating oil fractions; - . b) paraffins separated from these paraffin-containing lubricating oil fractions; c) of lubricating oil fractions obtained by hydrogenating splitting separated paraffins; and d) Mixtures of two or more of the mixtures of heavy compounds described above under a, b and c Hydrocarbons. 16. The method according to claim 1 to 15, characterized in that lubricating oils with a high viscosity index by hydrogenating cleavage of a mixture of heavy hydrocarbons at temperatures from 325 to 450 ⁰ C, pressures from 10 to 250 bar, room flow velocities from 0.2 to 5.0 kg feed per 1 catalyst per hour and ratios of hydrogen / feed from 100 to ■ 5 0.9-8 25/09 6.9 - 48 5000 Nl hydrogen per kg feed can be produced. 17. The method according to claim 16, characterized in that the lubricating oil production at temperatures of 350 to 425 ⁰ C, pressures from 100 to 200 bar, room flow rates of 0.5 to 1.5 kg feed per 1 catalyst per hour and proportions of hydrogen / Feeding of 500 to 2500 Nl of hydrogen per kg of feed is carried out. 18. The method according to claim 1 to 17, characterized in that that a lubricating oil with a high viscosity index by hydrotreating a mixture of heavy hydrocarbons and subsequent re-hydrogenation of the product obtained in the hydrogenating cleavage is produced. 19. The method according to claim 1 to 18, characterized in that a lubricating oil with a high viscosity index by hydrogenating columns. A mixture of heavy hydrocarbons, separating the product withdrawn from the hydrocracking reactor, or, if post-hydrogenation is used, that from the post-hydrogenation reactor withdrawing product, by distillation into one or more light fractions and a residue fraction with an initial boiling point of 350 to 550 ⁰ C, dewaxing the residue fraction and recycling at least part of the separated paraffins to the hydrocracking reactor. • '* 5 09825/0 969 20. The method according to claim 1 Ms 11, characterized in that light hydrocarbons by hydrogenating cleavage a mixture of heavy hydrocarbons are produced, 21. The method according to claim 1 to 5 and'11, characterized in that for the production of light hydrocarbons by hydrogenating cleavage of a mixture of heavy hydrocarbons, a catalyst is used which has been produced via the xerogel route and which contains 10 to 20 parts by weight of fluorine contains per 100 parts by weight of aluminum oxide. ■ ~ ■ 22. The method according to claim 1 and 6 to 11, characterized in that in the production of light hydrocarbons by hydrogenating cleavage of a mixture of heavy hydrocarbons, a catalyst is used which has been produced via the hydrogel route and which contains 20 to 30 parts by weight of fluorine per 100 Contains parts by weight of aluminum oxide. . 5098 Zt / 0 96 9